Mixtures of monoazo dyestuffs

ABSTRACT

The mixture of monoazo dyestuffs which contains one or more dyestuffs of the formula I    &lt;IMAGE&gt;  (I)  and one or more dyestuffs of the formula II    &lt;IMAGE&gt; (II)  wherein R1 and R2 independently of one another denote linear or branched alkyl with 1 to 6 carbon atoms and R denotes linear or branched alkyl with 1 to 3 carbon atoms, is outstandingly suitable for dyeing and printing hydrophobic materials a deep blue color.

The invention relates to mixtures of monoazo dyestuffs, which arecharacterized in that they consist of one or more dyestuffs of theformula I ##STR3## and one or more dyestuffs of the formula II ##STR4##wherein R¹ and R² independently of one another denote Linear or branchedalkyl with 1 to 6 C atoms and R denotes linear or branched alkyl with 1to 3 C atoms.

The invention also relates to processes for the preparation of thedyestuff mixtures according to the invention and thier use for dyeingand printing hydrophobic fibre materials.

It is already known that mixtures of at least two different individualdyestuffs of the formula I have improved dyeing properties in comparisonwith the individual dyestuffs (compare German Auslegeschrift No.2,234,465 (corresponding to U.S. Pat. No. 3,954,395), European Pat. No.93,933 and German Offenlegungsschrift 3,347,572, corresponding to U.S.Pat. No. 4,689,050.

It has now been found, surprisingly, that the mixtures according to theinvention have considerably improved dyeing properties in comparisonwith the individual dyestuffs and in some cases also in comparison withthe mixtures of German Auslegeschrift No. 2,234,465 and European Pat.No. 93,935.

The dyestuff mixtures according to the invention consist of one or moredyestuffs of the formula I and one or more dyestuffs of the formula II.Dyestuff mixtures according to the invention which consist of one or twodyestuffs each of the formulae I and II are preferred.

Dyestuff mixtures which consist of dyestuffs of the formulae I and IIwherein R¹ and R² denote linear alkyl with 2 to 4 C atoms and R denoteslinear or branched akyl with 1 to 3 C atoms are also preferred. Dyestuffmixtures which consist of dyestuffs of the formulae I and II wherein R¹and R² in one dyestuff are in each case identical and denote n-proplyand, in particular, ethyl and which contain one or more dyestuffs of theformula I in which R denotes methyl, i-propyl or, in particular,n-propyl are those which contain at least 2 dyestuffs of the formula Iin which the radicals R are different and two of these dyestuffs havethe combinations, CH₃ /i-C₃ H₇, C₂ H₅ /i-C₃ H₇, C₂ H₅ /n-C₃ H₇, i-C₃ H₇/n-C₃ H₇ or, in particular, CH₃ /n-C₃ H₇ for R, the radicals R¹ and R²of all the dyestuffs of these mixtures representing linear alkly with 2to 4 C atoms, and are preferably identical in each individual dyestuffand are especially preferably ethyl.

Dyestuff mixtures which contain at least 2 dyestuffs of the formula I inwhich the radicals R are in each case identical and denote ethyl,n-propyl, i-propyl or, in particular, methyl and the radicals R¹ and R²,which are preferably identical in each of the individual dyestuffs,differ from dyestuff to dyestuff and have the combinationsethyl/n-butyl, propyl/-n-butyl or, in particular, ethyl/n-propyl, arefurthermore preferred.

Mixtures which contain the dyestuff of the formula II known and where R¹=R² =ethyl and the dyestuffs of the formula I where R¹ =R² =ethyl and R=methyl or n-propyl, or the dyestuffs of the formula I where R=methyland R¹ =R² =ethyl or n-propyl, or, in particular, the dyestuff of theformula I where R¹ =R² =ehtyl and R=n-propyl, are especially preferred.

In the dyestuff mixtures according to the invention, the ratio of thevarious dyestuffs of the general formulae I and II can vary withinrelatively wide limits. In general, the minimum proportion by weight ofone component is 10% and the maximum proportion by weight is 90%. Indyestuff mixtures which consist only of two dyestuffs of the generalformulae I and II, an amount ratio of 70/30 to 30/70 is preferred, thatis to say the proportion by weight of one dyestuff is 30 to 70%.

The individual dyestuffs of the formulae I and II are known anddescribed, for example, in German Patent Specification No. 1,794,402(corresponding to U.S. Pat. Nos. 3,962,209; 4,105,655 and 4,237,048) andEuropean Patent Specification No. 36,512 (corresponding to U.S. Pat. No.4,381,262).

The dyestuff mixtures according to the invention can be prepared byvarious processes.

1. By mixing the separately prepared and separately finished individualdyestuffs. This mixing process is carried out in suitable mixers, suchas, for example, tumbler mixers.

2. By diazotization and common coupling, characterized in that an amineof the formula III ##STR5## is diazotized and the diazotization productis coupled to a mixture of in each case at least one coupling componentof the formulae IV or V ##STR6## in which R¹, R² and R independently ofone another have the abovementioned meanings. The composition of themixture of the coupling components is thereby chosen such that thedyestuff mixtures according to the invention are formed. Thediazotization and coupling are thereby carried out in a manner which isknown per se, such as is customary for the preparation of individualdyestuffs and is described, for example, in Czech Patent SpecificationNo. 164,657. The dyestuff mixtures thus prepared are then finishedtogether.

Preferably 3: by common cyano exchange, characterized in that indyestuff mixtures which consist of at least one dyestuff of the formulaVI and at least one dyestuff of the formula VII ##STR7## in which Zrepresents cyano or halogen and Hal represents halogen, preferablybromine, and R¹, R² and R have the abovementioned meanings, halogen isexchanged for cyano in a manner which is known per se, such as isdescribed for individual dyestuffs, for example in British PatentSpecification No. 1,125,685. The composition of the mixture of thedyestuffs of the formulae VI and VII is thereby chosen such thatdyestuff mixtures according to the invention are formed.

The mixture of the dyestuffs of the formulae VI and VII can be preparedby mixing the individual dyestuffs of the formulae VI and VII. However,they can also be obtained by diazotizing a diazo component of thegeneral formula VIII ##STR8## in which Z represents cyano or halogen andHal represents bromine or chlorine, and Z and Hal preferably representbromine, and coupling the diazotization product to a mixture of thecoupling components of the general formulae IV and V.

Preferably 4: by common finishing of the separately prepared individualcomponents.

This common finishing is characterized in that a dyestuff mixture of ineach case at least one dyestuff of the general formulae I and II isground in suitable mills, such as, for example, ball or sand mills, inthe presence of dispersing agents and, if a pulverulent finisheddyestuff is to be prepared, the mixture is then spray-dried.

Suitable dispersing agents are, for example, anionic or non-ionicdispersing agents, which can also be used together. Anionic dispersingagents are, for example, condensation products of aromatic sulphonicacids and formaldehyde, in particular condensation products ofalkylnaphthalenesulphonic acids and formaldehyde, condensation productsof optionally substituted phenol with formaldehyde and sodiumbisulphite, alkali metal salts of condensation products of optionallysubstituted phenol, naphthalene-or naphtholsulphonic acids, formaldehydeand sodium bisulphite, alkali metal salts of condensation products ofoptionally substituted phenolsulponic acids, formaldehyde and urea, andalkali metal salts of ligninsulphonic acids; alkyl- oralkyl-aryl-sulphonates and alkyl-aryl-polyglycol ether-sulphates.Non-ionic dispersing agents or emulsifiers are, for example, reactionproducts of alkylene oxides, such as, for example, ethylene oxide orpropylene oxide, with compounds which can be alkylated, such as, forexample, fatty alcohols, fatty amines, fatty acids, phenols,alkylphenols, arylalkylphenols, arylalkylarylphenols and carboxylic acidamides, such as, for example, addition products of 5 to 10 units ofethylene oxide on C₈ -C₁₀ -alkylphenols.

Grinding is carried out at temperatures between 10° and 90° C.,preferably at 30° to 60° C. In the case of common finishing ofseparately prepared individual components, common grinding attemperatures above 30° C. is advantageous. The dyestuff particles arethereby comminuted mechanically so that an optimum specific surface areais achieved and sedimentation of the dyestuff is as low as possible. Theparticle sizes of the dyestuffs are in general between 0.5 and 5 μm,preferably about 1 μm.

It is advantageous for the separately prepared individual components ofthe dyestuff mixture to be subjected to a common heat treatment beforethe common grinding. This heat treatment is characterized in that theindividual components of the dyestuff mixture are heated at temperaturesof 70° to 150° C., preferably 90° to 130° C., if appropriate underpressure, in water for half an hour to several hours and are then coledagain.This heating is advantgeously carried out in the presence of oneor more dispersing agents or an organic solvent. Examples of suchsolvents are methanol, ethanol, dimethylformamide or dimethylsulphoxide, but preferably solvents of low water-solubility, such astoluene, chlorobenzene, 1,2-dichlorobenzene or butyl acetate. Thesesolvents are distilled off again after the heat treatment.

A preferred pretreatment of the individual components of the dyestuffmixture before common grinding is common dissolving of the individualcomponents in an organic solvent or solvent mixture with subsequentcrystallization or precipitation, isolation, for example by filtration,and removal of solvent residues, for example by washing.

The dyestuff dispersions thus obtained can very advantageously be usedfor preparation of printing pastes and dye liquors. They offerparticular advantages, for example, in continuous processes in which thedyestuff concentration of the dye liquors must be kept constant bycontinuous feeding of dyestuff into the running apparatus.

Powder formulations are prefered for certain fields of use. Thesepowders contain the dyestuff, dispersing agents and other auxiliaries,such as, for example, wetting agents, oxidizing agents, preservativesand dust removal agents. A preferred process for the preparation ofpulverulent dyestuff formulations comprises removing the liquid from theliquid dyestuff dispersions described above, for example by vacuumdrying, freeze-drying, drying on roller driers or, preferably,spray-drying.

The dyestuff contents of the liquid dyestuff formulations are 20 to 40%.The dispersing agent contents are about 10 to 40%. In powderformulations, the dyestuff contents are 20 to 60% and the dispersingagent contents are 40 to 80%. For economic reasons, the dyestuff contentusually does not fall below 20%.

The dyestuff mixtures according to the invention are outstandinglysuitable as such, or as a mixture with other disperse dyestuffs, fordyeing and printing hydrophobic synthetic fibre materials. Surprisingly,they are superior to the individual dyestuffs in respect of dyeingproperties and coloristic fastnesses, such as, for example,thermomigration, fastness to thermofixing and fastness to water, washingand rubbing, in particular in build-up and exhaustion, and in levellingcapacity. Moreover, outstandingly deep dyeings with excellent exhaustionof the bath are still obtained with the dyestuff mixtures according tothe invention even when the dyeing temperatures are reduced and thedyeing time is shortened.

Possible hydrophobic synthetic materials are, for example; secondarycellulose acetate, cellulose triacetate, polyamides and, in particular,high molecular weight polyesters, such as, for example, polyethyleneglycol terephthalate and mixtures thereof with natural fibre materials,such as, for example, cotton, regenerated cellulose fibres or wool.

To prepare the dye liquors, the required amounts of the dyestuffformulations which have been prepared in accordance with the abovestatements are diluted with the dyeing medium, preferably with water, sothat a liquor ratio of 5:1 to 50:1 results for dyeing.

Other dyeing auxiliaries, such as dispersing agents, wetting agents andfixing auxiliaries, are in general also added to the liquors.

If the dyestuff is to be used for textile printing, the required amountsof the dyestuff formulations are kneaded together with thickeners, suchas, for example, alkali metal alginates or the like, and if appropriateother additives, such as, for example, fixation accelerants, wettingagents and oxidizing agents, to form printing pastes.

The invention is illustrated in more detail by the following examples:

EXAMPLE 1

14.7 g of the dyestuff of the formula IX ##STR9## 9.5 g of the dyestuffof the formula X ##STR10## and 5.1 g of the dyestuff of the formula XI##STR11## are homogenized together with 227.6 g of water, 86.8 g of ahigher molecular weight ligninsulphonate and 6.3 g of an arylpolyglycolether using a dissolver disc, and the pH is brought to 8.0 with 2.6 mlof 50% strength acetic acid. This mixture is then ground down to a finedivision of <5 μm in a water-cooling bead mill and the resulting groundpaste is sieved to remove the grinding agent and then dried with aspray-drier.

1.25 g of the dyestuff thus obtained are dispersed in 2,000 g of water.4 g of ammonium sulphate, 2 g of a commercially available dispersingagent based on a condensation product of sodium naphthalenesulphonateand formaldehyde and 2 g of a condensation product of m-cresol,formaldehyde and sodium sulphite are added to the dispersion and the pHis brought to 5.5 with acetic acid. 100 g of a texturized polyesterfabric based on polyethylene glycol terephthalate are introduced intothe dye liquor thus obtained and dyeing is carried out at 120° C. for1/2 hour. After subsequent rinsing, reductive after-treatment with a0.2% strength sodium dithionite solution at 70° to 80° C. for 15minutes, rinsing and drying, a deep blue dyeing with outstandingcoloristic properties is obtained.

If a further 100 g of a texturized polyester fabric based onpolyethylene glycol terephthalate is introduced into the dyebath tocarry out an exhaustion test, dyeing is carried out at 135° C. for 1hour and the fabric from the exhaustion test is after-treated asdescribed for the actual dyeing, an almost colourless dyeing isobtained.

EXAMPLE 2

In each case 14.7 g of the dyestuffs of the formulae IX and XI arebrought to a pH of 5.9 together in 243.7 g of water with 43.6 g ofsodium ligninsulphonate and 12.6 g of a non-ionic dispersing agent basedon arylpolyglcol ether (4-((4'benzyl-) phenyl)-phenol+15 ethylene oxideunits) using 50% strength acetic acid and are homogenized with a toothedstirrer. The resulting dispersion is then heated to 100° C. in anautoclave in the course of 2 hours and stirred at this temperature for 2hours. After cooling, 43.6 g of a condensation product of cresol,formaldehyde and sodium naphthol-2-sulphonate are added and thedispersion is brought to pH 8.0 with 50% strength acetic acid. Themixture is then ground down to a fine division (80%≦1 μm) in a bead millat room temperature for 2 hours, sieved and sprayed in a spray-drier.The dyestuff powder is then used for dyeing.

0.12 g of the dyestuff powder thus prepared is stirred into 250 ml ofwater, 0.4 g of a commercially available dispersing agent based on acondensation product of m-cresol, formaldehyde and sodium sulphite, 0.8g of a commercially available carrier based on methylnaphthalene, 0.8 gof crystalline sodium acetate and 1.2 ml of 30% strength acetic acid areadded, with stirring, and the mixture is made up to 400 ml with water.The pH of the dyebath is 4.5. 10 g of a polyester fabric based onpolyethylene glycol terephthalate are introduced into this dyebath. Thefabric is dyed at 95° C. in an open vessel for 90 minutes and the dyedmaterial is removed, rinsed, reduction cleared with alkaline 0.2%strength sodium dithionite solution (15 minutes at 60° to 70° C.),rinsed again and dried. A deep blue dyeing with outstanding coloristicproperties is thereby obtained.

Material dyed in an exhaustion test at 135° C. for 1/2 hour is almostcolourless.

EXAMPLE 3

17.6 g of the dyestuff of the formula IX and 11.7 g of the dyestuff ofthe formula X are converted into a dyestuff powder as described inExample 1.

0.12 g of the dyestuff powder thus prepared is stirred into 200 ml ofwater, and 0.2 g of a commercially available dispersing agent based on acondensation product of m-cresol, formaldehyde and sodium sulphite, 0.3g of a commercially available carrier based on methylnaphthalene, 0.4 gof crystalline sodium acetate and 1.2 ml of 30% strength acetic acid areadded, with stirring. The pH of the dyebath is 4.5. 10 g of a polyetersfabric based on polyethylene glycol terephthalate are introduced intothis dyebath and dyeing is carried out in a dyeing bomb at 106° C. underpressure for one hour. The fabric is finished, as described above, byrinsing, reductive after-treatment, renewed rinsing and drying and adeep blue dyeing with very good coloristic fastness properties islikewise obtained.

The following table gives other dyestuff mixtures according to theinvention which have the meanings of R, R¹ and R² and the weight ratioof the individual dyestuffs shown, and can be prepared in accordancewith the above statements and likewise give deep blue dyeings or printssimilarly with very good coloristic properties on polyester materials.

    ______________________________________                                        EXAM-  DYE-                           WEIGHT                                  PLE    STUFF    R.sup.1  R.sup.2                                                                              R     RATIO                                   ______________________________________                                        4      I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   80                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    20                                      5      I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            20                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   20                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    60                                      6      I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                     50                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    50                                      7      I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                   70                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    30                                      8      I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            331/3                                          I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                   331/3                                          II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    331/3                                   9      I        C.sub.2 H.sub.5                                                                        C.sub. 2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                     10                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   40                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    50                                      10     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                     40                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                   40                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    20                                      11     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            20                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                     20                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    60                                      12     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   30                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                   30                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    40                                      13     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            20                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   20                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub. 5                                                                     i-C.sub.3 H.sub.7                                                                   20                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    40                                      14     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            10                                             I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            30                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    60                                      15     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            20                                             I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            20                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    60                                      16     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            35                                             I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            35                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    30                                      17     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                     40                                             I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    C.sub.2 H.sub.5                                                                     20                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    40                                      18     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   60                                             I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7                                                                   10                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    30                                      19     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   30                                             I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            30                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    40                                      20     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                     60                                             I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            30                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    10                                      21     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                   30                                             I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            30                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    40                                      22     I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            40                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    60                                      23     I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            25                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    75                                      24     I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7                                                                   50                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    50                                      25     I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    C.sub.2 H.sub.5                                                                     65                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    35                                      26     I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    i-C.sub.3 H.sub.7                                                                   40                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    60                                      27     I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7                                                                   10                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   15                                             I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            10                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            10                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    55                                      28     I        n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                    CH.sub.3                                                                            50                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    50                                             I        n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                     45                                      29     II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    55                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            30                                      30     I        n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                    CH.sub.3                                                                            10                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    60                                      31     I        n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                    CH.sub.3                                                                            5                                              I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   55                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    40                                      32     I        n-C.sub.5 H.sub.11                                                                     n-C.sub.5 H.sub.11                                                                   CH.sub.3                                                                            30                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    70                                      33     I        n-C.sub.6 H.sub.13                                                                     n-C.sub.6 H.sub.13                                                                   CH.sub.3                                                                            25                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    75                                      34     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   45                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    55                                      35     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            70                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    30                                      36     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub. 5                                                                     CH.sub.3                                                                            30                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   10                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    60                                      37     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                     60                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    40                                      38     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                   50                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    50                                      39     I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            20                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    80                                      40     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            25                                             I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            25                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    50                                      41     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            30                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                   40                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    30                                      42     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            30                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                     30                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    40                                      43     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   70                                             II       n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                    --    30                                      44     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            45                                             II       n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                    --    55                                      45     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            25                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   50                                             II       n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                    --    25                                      46     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            30                                             I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   30                                             II       n-C.sub.5 H.sub.11                                                                     n-C.sub.5 H.sub.11                                                                   --    40                                      47     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            65                                             I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            15                                             II       n-C.sub.6 H.sub.13                                                                     n-C.sub.6 H.sub.13                                                                   --    20                                      48     I        CH.sub.3 CH.sub.3                                                                             C.sub.2 H.sub.5                                                                     50                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    50                                      49     I        CH.sub.3 CH.sub.3                                                                             n-C.sub.3 H.sub.7                                                                   35                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    65                                      50     I        CH.sub.3 CH.sub.3                                                                             CH.sub.3                                                                            331/3                                          I        CH.sub.3 CH.sub.3                                                                             n-C.sub.3 H.sub.7                                                                   331/3                                          II       CH.sub.3 CH.sub.3                                                                             --    331/3                                   51     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   75                                             II       CH.sub.3 CH.sub.3                                                                             --    25                                      52     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            30                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    35                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    35                                      53     I        C.sub.2 H.sub. 5                                                                       C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                     30                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    45                                             II       n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                    --    25                                      54     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   50                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    25                                             II       n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                    --    25                                      55     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   35                                             II       CH.sub.3 CH.sub.3                                                                             --    30                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    35                                      56     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   20                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    40                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    40                                      57     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                     25                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    50                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    25                                      58     I        C.sub.2 H.sub. 5                                                                       C.sub.2 H.sub.5                                                                      i-C.sub.3 H.sub.7                                                                   50                                             II       CH.sub.3 CH.sub.3                                                                             --    25                                             II       n-C.sub.4 H.sub.9                                                                      n-C.sub.4 H.sub.9                                                                    --    25                                      59     I        C.sub.2 H.sub.5                                                                        n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            331/3                                          II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    662/3                                   60     I        CH.sub.3 n-C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                     50                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    50                                      61     I        CH.sub.3 n-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7                                                                   45                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    55                                      62     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            40                                             II       C.sub.2 H.sub.5                                                                        n-C.sub.3 H.sub.7                                                                    --    60                                      63     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                     50                                             II       CH.sub.3 n-C.sub.3 H.sub.7                                                                    --    50                                      64     I        C.sub.2 H.sub.5                                                                        i-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            30                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      70                                            65     I        C.sub.2 H.sub.5                                                                        i-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7                                                                   35                                             II       C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      --    65                                      66     I        CH.sub.3 i-C.sub.3 H.sub.7                                                                    C.sub.2 H.sub.5                                                                     50                                             II       n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    --    50                                      67     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      CH.sub.3                                                                            40                                             II       CH.sub.3 i-C.sub.3 H.sub.7                                                                    --    60                                      68     I        n-C.sub.3 H.sub.7                                                                      n-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            35                                             II       C.sub.2 H.sub.5                                                                        i-C.sub.3 H.sub.7                                                                    --    65                                      69     I        C.sub.2 H.sub.5                                                                        i-C.sub.3 H.sub.7                                                                    C.sub.2 H.sub.5                                                                     60                                             II       C.sub.2 H.sub.5                                                                        i-C.sub.3 H.sub.7                                                                    --    40                                      70     I        C.sub.2 H.sub.5                                                                        i-C.sub.3 H.sub.7                                                                    CH.sub.3                                                                            40                                             I        C.sub.2 H.sub.5                                                                        i-C.sub.3 H.sub.7                                                                    n-C.sub.3 H.sub.7                                                                   40                                             II       C.sub.2 H.sub.5                                                                        i-C.sub.3 H.sub.7                                                                    --    20                                      71     I        CH.sub.3 i-C.sub.4 H.sub.9                                                                    C.sub.2 H.sub.5                                                                     331/3                                          II       CH.sub.3 i-C.sub.4 H.sub.9                                                                    --    331/3                                          II       C.sub.2 H.sub.5                                                                        i-C.sub.4 H.sub.9                                                                    --    331/3                                   72     I        C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                      n-C.sub.3 H.sub.7                                                                   50                                             II       CH.sub.3 i-C.sub.5 H.sub.11                                                                   --    50                                      ______________________________________                                    

What is claimed is:
 1. A mixture of monoazo dyestuffs which comprisesone or more dyestuffs of the formula I ##STR12## and one or moredyestuffs of the formula II ##STR13## wherein R¹ and R² independently ofone another each denote linear or branched alkyl with 1 to 6 carbonatoms and R denotes linear or branched alkyl with 1 to 3 carbon atoms.2. A dyestuff mixture according to claim 1 wherein the weight proportionof a dyestuff of the formula I or II is 10 to 90%.
 3. A dyestuff mixtureaccording to claim 1 wherein the weight proportion of a dyestuff of theformulae I or II is 30 to 70%.
 4. A dyestuff mixture according to claim1 which contains one or two dyestuffs each of the formulae I and II. 5.A dyestuff mixture according to claim 1 wherein R¹ and R² denote linearalkyl with 2 to 4 carbon atoms and R denotes alkyl 1 to 3 carbon atoms.6. A dyestuff mixture according to claim 1 wherein at least one of thedyestuffs or the formulae I or II has for both R¹ and R² n-propyl andwhich contains one or more dyestuffs of the formula I in which R denotesmethyl, i-propyl or n-propyl.
 7. A dyestuff mixture according to claim 6wherein R is n-propyl.
 8. A dyestuff mixture according to claim 1wherein at least one of the dyestuffs of the formulae I or II has forboth R¹ and R² ethyl and which contains one or more dyestuffs of theformula I in which R denotes methyl, i-propyl or n-propyl.
 9. A dyestuffmixture according to claim 8 wherein R is n-propyl.
 10. A dyestuffmixture according to claim 1 which contains at least two dyestuffs ofthe formula I in which the R moieties are different and two of thesedyestuffs have for R the combinations methyl/i-propyl, ethyl/i-propyl,ethyl/n-propyl, i-propyl/n-propyl or methyl/n-propyl.
 11. A dyestuffmixture according to claim 10 wherein the two dyestuffs of the formula Idenote R as methyl/n-propyl.
 12. A dyestuff mixture according to claim10 wherein R¹ and R² are the same moiety.
 13. A dyestuff mixtureaccording to claim 10 wherein R¹ and R² are both ethyl.
 14. A dyestuffmixture according to claim 2 which contains at least two dyestuffs ofthe formula I in which the R moieties are in each identical and denotemethyl, ethyl, n-propyl or i-propyl and the R¹ and R² moieties areidentical on each individual dyestuff of formula I or II but differ fromdyestuff I to dyestuff II and have the combinations ethyl/n-butyl,propyl/n-butyl or ethyl/n-propyl.
 15. A deystuff mixture according toclaim 14 wherein R is methyl and R¹ /R² is ethyl/n-propyl.
 16. Adeystuff mixture according to claim 1 wherein for the dyestuff offormula II, R¹ and R² are both ethyl and in the dyestuffs of formula IR¹ and R² and ethyl or n-propyl and R is methyl or n-propyl.
 17. Adyestuff mixture according to claim 16 wherein for the dyestuff offormula I, R¹ and R² are both ethyl and R is n-propyl.
 18. Process forthe preparation of the dyestuff mixture according to claim 1 whichcomprises diazotizing an amine of the formula ##STR14## and coupling thediazotized amine to a mixture of coupling components of the formulae##STR15##
 19. Process for the preparation of the dyestuff mixtureaccording to claim 1 wherein a dyestuff mixture of at least one dyestuffof each of the formulae ##STR16## wherein Z represents cyano or halogenand Hal represents halogen, is subjected to cyano replacement ofhalogen.
 20. In the process for dyeing and printing hydrophobic fibermaterials and mixtures thereof with natural fibers or regeneratedcellulose fibers by applying thereto an azo dyestuffs,The improvementcomprises said azo dyestuff being a dyestuff mixture according to claim1.